Photoprotective/cosmetic compositions comprising 2,4,6-tris[p-((2&#39;-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazine and dioctyl malate

ABSTRACT

Topically applicable sunscreen/cosmetic compositions having improved cosmetic properties and well suited for enhanced photoprotection of human skin and/or hair against the damaging effects of UV-A and UV-B irradiation, particularly solar radiation, comprise (i) a photoprotecting effective amount of 2,4,6-tris[p-((2&#39;-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazine and (ii) the oil dioctyl malate, in an amount effective to itself substantially dissolve the total amount of triazine compound (i), in a cosmetically acceptable vehicle, diluent or carrier therefor.

CROSS-REFERENCE TO COMPANION APPLICATIONS

Copending applications Ser. No. 08/463,221 [Attorney Docket No.016800-028], Ser. No. 08/463,221 [Attorney Docket No. 016800-029], Ser.No. 08/463,505 [Attorney Docket No. 016800-031], Ser. No. 08/463,762[Attorney Docket No. 016800-032], Ser. No. 08/463,304 [Attorney DocketNo. 016800-033], Ser. No. 08/463,508 [Attorney Docket No. 016800-034],Ser. No. 08/461,015 [Attorney Docket No. 016800-035], Ser. No.08/463,507 [Attorney Docket No. 016800-036], Ser. No. 08/464,940 eachfiled concurrently herewith and each assigned to the assignee hereof.

BACKGROUND OF THE INVENTION

1. Technical Field of the Invention

The present invention relates to novel cosmetic compositions for topicalapplication, for the photoprotection of the skin and/or the hair againstultraviolet radiation (such compositions hereinafter simply designated"sunscreen," "sunscreen/cosmetic" or "photoprotective/sunscreen"compositions), and to the use of same for the cosmetic applicationsindicated above.

This invention more especially relates to the aforesaidsunscreen/cosmetic compositions imparting enhanced photoprotection andexhibiting improved cosmetic properties, comprising, in a cosmeticallyacceptable vehicle, carrier or diluent, typically an oil-in-wateremulsion, combinatory immixture of (i) the lipophilic organic sunscreencompound2,4,6-tris[p-((2'-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazine and(ii) a judiciously selected specific oil, present in a predeterminedamount, namely, dioctyl malate.

2. Description of the Prior Art

It is well known to this art that light radiation of wavelengths of from280 nm to 400 nm promotes tanning of the human epidermis, and thatirradiation of wavelengths of from 280 to 320 nm, i.e., UV-Birradiation, causes erythema and burning of the skin which can impairthe development of a natural tan; hence, such UV-B radiation must thusbe screened from the skin.

It is also known to this art that UV-A radiation, of wavelengths from320 to 400 nm, which tans the skin, also adversely affects it, inparticular in the event of sensitive skin or a skin which is continuallyexposed to solar radiation.

UV-A rays cause, in particular, a loss in the elasticity of the skin andthe appearance of wrinkles, promoting a premature aging thereof. Suchirradiation promotes triggering of the erythematous reaction or enhancesthis reaction in certain individuals, and may even be the source ofphototoxic or photoallergic reactions. Thus, it is desirable to alsoscreen out UV-A radiation.

A wide variety of cosmetic compositions intended for the photoprotection(UV-A and/or UV-B) of human skin are known to this art.

These photoprotective/sunscreen compositions are typically oil-in-wateremulsions (namely, a cosmetically acceptable vehicle, carrier or diluentcomprising an aqueous continuous dispersing phase and an oilydiscontinuous dispersed phase) which contains, in variousconcentrations, one or more standard lipophilic and/or hydrophilicorganic sunscreen compounds capable of selectively absorbing harmful ordeleterious UV radiation. These sunscreen compounds (and the amountsthereof) are selected as a function of the desired sun protection factor(the sun protection factor (SPF) being expressed mathematically by theratio of the irradiation time required to attain the erythema-formingthreshold with the UV screening agent to the time required to attain theerythema-forming threshold in the absence of UV screening agent).

One organic sunscreen compound having desirable properties and which todate has been widely used is2,4,6-tris[p-((2'-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazine, alipophilic sunsceen compound which is highly active in the UV-B range,photostable and water-resistant. This compound is marketed under thetrademark "UVINUL T 150" by BASF. Nonetheless, in the absence ofreinforcement provided by other sunscreen agents, its photoprotectivepower is fairly limited in the usual cosmetic vehicles containing oils,such as oxyethylenated or oxypropylenated fatty mono- or polyalcohols("Cetiol HE" marketed by Henkel or "Witconol APM" marketed by Witco). Inaddition, the cosmetic properties associated therewith are generallyregarded as unsatisfactory.

SUMMARY OF THE INVENTION

It has now unexpectedly and surprisingly been determined that thephotoprotective power and cosmetic properties of2,4,6-tris[p-((2'-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazine areconspicuously improved by formulating same with a particular oil, i.e.,dioctyl malate, in an amount such that said dioctyl malate is itselfcapable of dissolving the entirety of said lipophilic triazine sunsceen.

Briefly, the present invention features novel photoprotective/cosmeticcompositions comprising, in a cosmetically acceptable vehicle, diluentor carrier, (i) an effective sunscreen amount of2,4,6-tris[p-((2'-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazine, and(ii) an amount of dioctyl malate effective to itself dissolve the totalamount of said triazine compound (i).

The present invention also features the use of such compositions as, orfor the formulation of, sunscreen/cosmetic compositions intended for thephotoprotection of the skin and/or the hair against ultravioletirradiation, in particular solar radiation.

The cosmetic treatment for the photoprotection of the skin and/or thehair against ultraviolet irradiation, in particular solar radiation,comprises topically applying thereto an effective amount of asunscreen/cosmetic composition as described above.

This invention, thus, also features the use of dioctyl malate forimproving the photoprotective capacity and/or cosmetic properties ofsunscreen/cosmetic compositions comprised of2,4,6-tris[p-((2'-ethylhexyl)oxycarbonyl)anilino]-1,3,5triazine.

DETAILED DESCRIPTION OF BEST MODE AND PREFERRED EMBODIMENTS OF THEINVENTION

More particularly according to the present invention,2,4,6-tris[p-((2'-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazine(compound A) is a sunscreen compound that is per se known to this artand is active in the UV-B range, is a solid material and is marketedunder the trademark "UVINUL T 150" by BASF. This compound has thefollowing structural formula (I): ##STR1## in which R is a 2-ethylhexylradical.

The triazine sunscreen compound (i) is advantageously present in thecompositions according to the invention at a concentration ranging from0.1% to 10% by weight, and preferably from 0.5% to 5% by weight,relative to the total weight of the composition. In an importantembodiment of this invention, said triazine compound (i) must exist inthe final sunscreen/cosmetic compositions in an entirely, orsubstantially entirely, dissolved state.

The dioctyl malate according to the present invention is a knowncompound, designated Dioctyl Malate in the CTFA nomenclature (5thedition, 1993), and which has the following structural formula (II):##STR2##

This compound is commercially available and is marketed under thetrademark "Ceraphyl 45" by Mallinckrodt.

This specific oil is advantageously present in the finalsunscreen/cosmetic compositions at a concentration ranging from 0.5% to50% by weight relative to the total weight of the composition, andpreferably from 2% to 30% by weight thereof. It is an essentialcharacteristic of the compositions according to the invention that thedioctyl malate must be present in an amount such that it itself issufficient to dissolve the total amount, or substantially total amount,of the 2,4,6-tris[p-((2'-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazinepresent therein. This minimum amount of solvent oil, intended to providefor the complete and stable dissolution of the solid sunscreen compound(i), can readily be conventionally determined from the solubilityparameters of said screening compound in this solvent.

Moreover, the concentrations and ratios of the sunscreen compound (i)and the oil (ii) are typically selected such that the sun protectionfactor of the final composition is preferably at least 2.

In a preferred embodiment of the present invention, the cosmeticallyacceptable vehicle, diluent, carrier or support in which the compound(i) and oil (ii) are formulated is an emulsion of oil-in-water type.

Of course, the sunscreen/cosmetic compositions according to theinvention may contain one or more additional hydrophilic or lipophilicsunscreen agents active in the UV-A and/or UV-B range (absorbers), otherthan the two sunscreen compounds indicated above. Exemplary of suchadditional sunscreens are cinnamic derivatives, salicylic derivatives,camphor derivatives, triazine derivatives, benzophenone derivatives,dibenzoylmethane derivatives, β,β-diphenylacrylate derivatives,p-aminobenzoic acid derivatives, and the sunscreen polymers andsunscreen silicones described in WO-93/04,665. Other examples of organicsunscreen agents are described in EO-A-0,487,404.

The compositions according to the invention may also contain agents forthe artificial tanning and/or browning of the skin (self-tanning agents)such as, for example, dihydroxyacetone (DHA).

The cosmetic compositions according to the invention may also containpigments or, alternatively, nanopigments (average size of the primaryparticles: generally ranging from 5 nm to 100 nm, preferably from 10 to50 nm) of coated or uncoated metal oxides such as, for example,nanopigments of titanium dioxide (amorphous or crystallized in rutileand/or anatase form), of iron oxide, of zinc oxide, of zirconium oxideor of cerium oxide, which are all photoprotective agents that are per sewell known to this art and which are effective by physical blocking(reflection and/or diffusion) of the UV irradiation. Conventionalcoating agents include, moreover, alumina and/or aluminum stearate. Suchcoated or uncoated metal oxide nanopigments are described, inparticular, in EP-A-0,518,772 and EP-A-0,518,773.

The compositions of the invention may additionally comprise conventionalcosmetic additives and adjuvants selected especially from among fats,organic solvents, ionic or nonionic thickening agents, softeners,antioxidants and especially anti-free-radical antioxidants, opacifyingagents, stabilizing agents, emollients, silicones, α-hydroxy acids,anti-foaming agents, hydrating agents, vitamins, fragrances,preservatives, surfactants, fillers, insect repellants, sequesteringagents, polymers, propellants, basifying or acidifying agents, dyes andcolorants, or any other ingredient usually employed in cosmetics, inparticular for the production of sunscreen/cosmetic compositions inemulsion form.

The fats may comprise an oil or a wax or mixtures thereof, and may alsocomprise fatty acids, fatty alcohols and fatty acid esters. The oils maybe selected from among animal, plant, mineral or synthetic oils and,especially, from among liquid petrolatum, paraffin oil, volatile ornon-volatile silicone oils, isoparaffins, poly-α-olefins, fluoro oilsand perfluoro oils. Similarly, the waxes may be selected from amonganimal, fossil, plant, mineral or synthetic waxes that are per se knownto this art.

Exemplary organic solvents include the lower polyols and alcohols.

The thickening agents may be selected, especially, from amongcrosslinked polyacrylic acids, modified or unmodified guar gums andcelluloses such as hydroxypropyl guar gum, methylhydroxyethylcelluloseand hydroxypropylmethylcellulose.

The compositions of the invention may be formulated according totechniques well known to this art, in particular those intended for thepreparation of emulsions of oil-in-water or water-in-oil type.

The subject compositions may, in particular, be in simple or complex(O/W, W/O, O/W/O or W/O/W) emulsion form such as a cream, a milk, a gel,an ointment or a cream gel, in powder form or in solid stick form andmay optionally be packaged as an aerosol and may be provided in the formof a foam or a spray.

When it is an emulsion, the aqueous phase of this emulsion may comprisea nonionic vesicle dispersion prepared according to known processes(Bangham, Standish and Watkins, J. Mol. Biol, 13, 238 (1965),FR-2,315,991 and FR-2,416,008).

The cosmetic compositions of the invention are useful for protecting thehuman epidermis or the hair against the damaging effects of ultravioletrays, as sunscreen compositions or as makeup products.

When the cosmetic compositions according to the invention are used forphotoprotection of the human epidermis against UV rays, or as sunscreencompositions, they may be formulated as a suspension or a dispersion insolvents or fats, in the form of a nonionic vesicle dispersion or,alternatively, in the form of an emulsion, preferably of oil-in-watertype, such as a cream or a milk, or in ointment, gel, cream gel, solidstick, stick, aerosol foam or spray form.

When the cosmetic compositions according to the invention are used forthe photoprotection of the hair, they may be formulated as a shampoo, alotion, a gel, an emulsion, a nonionic vesicle dispersion or a lacquerfor the hair and may constitute, for example, a composition to berinsed, to be applied before or after shampooing, before or after dyeingor bleaching, before, during or after permanent-waving orhair-straightening, a styling or treating lotion or gel, a blow-dryingor hair-setting lotion or gel, or a composition for the permanent-wavingor straightening, dyeing or bleaching of the hair.

When the subject compositions are used as a makeup product for theeyelashes, the eyebrows or the skin, such as an epidermal treatmentcream, a foundation, a lipstick, an eyeshadow, a blush, a mascara or"eyeliner", they may be in anhydrous or aqueous, solid or pasty form,such as oil-in-water or water-in-oil emulsions, nonionic vesicledispersions or, alternatively, suspensions.

For example, for the photoprotective/sunscreen formulations inaccordance with this invention which comprise a vehicle of oil-in-wateremulsion type, the aqueous phase (comprising hydrophilic sunscreenagents in particular) generally constitutes from 50% to 95% by weight,preferably from 70% to 90% by weight, relative to the total formulation,the oily phase (comprising lipophilic sunscreen agents in particular)from 5% to 50% by weight, preferably from 10% to 30% by weight, relativeto the total formulation, and the (co)emulsifying agent(s) from 0.5% to20% by weight, preferably from 2% to 10% by weight, relative to thetotal formulation. If desired, the fatty phase of the emulsionsaccording to the invention may comprise only the oil (ii), i.e., onlythe dioctyl malate.

The cosmetic treatment of the skin or hair to protect same against thedeleterious effects of UV rays, especially those contained in solarradiation, comprises applying thereto an effective amount of asunscreen/cosmetic composition as described above.

With respect to the compositions of the prior art containing2,4,6-tris[p-((2'-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazine, thecompositions in accordance with the invention, which contain the samesunscreen compound, but in immixture with a sufficient amount of dioctylmalate, exhibit a better spreadability and they are less sticky, lessgreasy and gentler on application thereof.

In order to further illustrate the present invention and the advantagesthereof, the following specific examples are given, it being understoodthat same are intended only as illustrative and in nowise limitative.

EXAMPLE 1

A variety of photoprotective/sunscreen formulations were prepared, inthe form of emulsions of oil-in-water type and which contained (theamounts are expressed in weight % with respect to the total weight ofthe composition):

    ______________________________________                                        (a) 2,4,6-Tris[p-((2'-ethylhexyl)-                                                                            10%                                               oxycarbonyl)anilino]-1,3,5-triazine                                           ("UVINUL T 150") (sunscreen)                                              (b) Crosslinked terpolymer: methacrylic                                                                       5%                                                acid/ethyl acrylate/steareth-10 allyl ether,                                  as a 30% aqueous emulsion ("SALCARE SC 90"                                    marketed by Allied Colloids) (emulsifier)                                 (c) oil                         20%                                           (d) Preservatives               qs                                            (e) Water                       qs 100%                                           with the nature of the oil being varied.                                  ______________________________________                                    

Each of these emulsions was produced by dissolving thephotoprotective/sunscreen agent in the fatty phase, then adding theemulsifier to this fatty phase, heated to approximately 80° C., and,lastly, adding, with rapid stirring, the aqueous phase which had beenheated beforehand to the same temperature.

For each of the formulations thus prepared, the sun protection factor(SPF) associated therewith was then determined. The SPF was determinedby using the in vitro technique described by B. L. Diffey et al, in J.Soc. Cosmet. Chem., 40, 127-133 (1989); this technique entaileddetermining the monochromatic protection factors every 5 nm over a rangeof wavelengths from 290 to 400 nm, and in calculating the sun protectionfactor from these factors according to a given mathematical equation.

The compositions of the various formulations examined and the resultsobtained, as a mean protection factor, are reported in Table I below:

Also, by way of comparison, the results obtained using an oil-freecomposition are reported:

                  TABLE I                                                         ______________________________________                                                          Mean SPF                                                                      (standard                                                   OIL               deviation)                                                  ______________________________________                                        Without           1.2                                                         PEG-7 Glyceryl Cocoate                                                                          3.8         Comparative                                     ("CETIOL HE" marketed by                                                                        (0.5)                                                       Henkel)                                                                       Diisopropyl Adipate                                                                             2.8                                                                           (0.1)                                                       Dioctyl Malate    6.8         Invention                                       ("CERAPHYL 45" marketed by                                                                      (0.9)                                                       Mallinckrodt)                                                                 ______________________________________                                    

These results clearly demonstrate the notable beneficial effectcontributed by the presence of the oil in accordance with the inventionto the sun protection factors of the final compositions.

Moreover, the cosmetic properties of the above composition in accordancewith the invention (UVINUL T 150+CERAPHYL 45) were compared with thoseof a comparative composition UVINUL T 150+CETIOL HE, also as preparedabove. These cosmetic properties were assessed by three human controls(sensory analysis test) by the application to their forearms of 0.2 g ofcomposition. These subjects then graded the effects obtained on the skinfrom 0 to 5, grade 5 being the maximum grade corresponding to thedesired criterion (less sticky, less greasy, more easily spread, and thelike). The means of the grades obtained (with their standard deviation)are reported in Table II below:

    ______________________________________                                                        Composition                                                                   according to the                                                                          Comparative                                       Cosmetic property                                                                             invention   composition                                       ______________________________________                                        Spreading on application                                                                      2.83 (0.76) 1.17 (0.29)                                       Greasy on application                                                                         2.83 (0.58) 2.33 (0.29)                                       Sticky on application                                                                         2.33 (0.29) 0.83 (0.76)                                       Brake           2.83 (0.29) 1.67 (0.29)                                       Overall preference                                                                            3.00 (0.5)  1.67 (0.58)                                       ______________________________________                                    

These results demonstrate the better cosmetic properties of thecompositions according to the invention.

EXAMPLE 2

A specific example of a photoprotective/sunscreen composition inaccordance with the invention, in the form of an oil-in-water emulsion,is as follows:

    ______________________________________                                        (a)  2,4,6-Tris[p-((2'-ethylhexyl)-                                                                           3.5 g                                              oxycarbonyl)anilino]-1,3,5-triazine                                           ("UVINUL T 150")                                                         (b)  4-tert-Butyl-4'-dibenzoylmethane                                                                         1 g                                                ("PARSOL 1789" marketed by Givauden)                                          (sunscreen)                                                              (c)  TiO.sub.2 of nanopigment grade                                                                           3 g                                                ("MT 100 T" marketed by Tayca)                                           (d)  Dioctyl Malate             10 g                                               ("CERAPHYL 45" marketed by                                                    Mallinckrodt)                                                            (e)  Mixture of cetylstearyl alcohol                                                                          7 g                                                and of cetylstearyl alcohol oxyethylenated with                               33 moles of EO (80%/20%)                                                      ("DEHSCO T 390" marketed by Tensia)                                      (f)  Mixture of glyceryl mono- and                                                                            2 g                                                distearate ("GELEOL COPEAUX" marketed                                         by Gattefosse)                                                           (g)  Cetyl alcohol              1.5 g                                         (h)  Polydimethylsiloxane ("SILBIONE                                                                          1.5 g                                              OIL 70 047V 300" marketed by Rhone-Poulenc)                              (i)  Liquid paraffin            10 g                                          (j)  Benzoates of C.sub.12 /C.sub.15 alcohols                                                                 4 g                                                ("FINSOLV TN" marketed by Finetex)                                       (k)  Ethylenediaminetetraacetic acid,                                                                         0.1 g                                              disodium salt-2H.sub.2 O ("EDETA BD" marketed                                 by BASF)                                                                 (l)  Glycerol                   20 g                                          (m)  Preservatives              qs                                            (n)  Fragrance                  qs                                            (o)  Water                      qs 100 g                                      ______________________________________                                    

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

What is claimed is:
 1. A topically applicable sunscreen/cosmeticcomposition adopted for the photoprotection of human skin and/or hair,comprising (i) a photoprotecting effective amount of2,4,6-tris[p-((2'-ethylhexyl)oxycarbonyl)anilino]-1,3,5-triazine and(ii) the oil dioctyl malate, in an amount effective to itselfsubstantially dissolve the total amount of said triazine compound (i),in a cosmetically acceptable vehicle, diluent or carrier therefor. 2.The sunscreen/cosmetic composition as defined by claim 1, comprisingfrom 0.1% to 10% by weight of said triazine compound (i).
 3. Thesunscreen/cosmetic composition as defined by claim 2, comprising from0.5% to 5% by weight of said triazine compound (i).
 4. Thesunscreen/cosmetic composition as defined by claim 2, comprising from0.5% to 50% by weight of said dioctyl malate (ii).
 5. Thesunscreen/cosmetic composition as defined by claim 3, comprising from 2%to 30% by weight of said dioctyl malate (ii).
 6. The sunscreen/cosmeticcomposition as defined by claim 1, comprising an oil-in-water emulsion.7. The sunscreen/cosmetic composition as defined by claim 1, comprisinga water-in-oil emulsion.
 8. The sunscreen/cosmetic composition asdefined by claim 1, further comprising at least one additionalhydrophilic or lipophilic organic UV-A and/or UV-B sunscreen.
 9. Thesunscreen/cosmetic composition as defined by claim 8, further comprisingat least one cinnamic derivative, salicylic derivative, camphorderivative, triazine derivative, benzophenone derivative,dibenzoylmethane derivative, β,β-diphenylacrylate derivative,p-aminobenzoic acid derivative, sunscreen polymer, or sunscreensilicone.
 10. The sunscreen/cosmetic composition as defined by claim 1,further comprising a photoprotecting effective amount of particulates ofat least one inorganic pigment or nanopigment.
 11. Thesunscreen/cosmetic composition as defined by claim 10, said at least onepigment or nanopigment comprising titanium dioxide, zinc oxide, ironoxide, zirconium oxide, cerium oxide, or mixture thereof.
 12. Thesunscreen/cosmetic composition as defined by claim 1, further comprisingat least one active agent for the artificial tanning and/or browning ofhuman skin.
 13. The sunscreen/cosmetic composition as defined by claim1, further comprising at least one cosmetically acceptable adjuvant oradditive.
 14. The sunscreen/cosmetic composition as defined by claim 13,said at least one adjuvant or additive comprising a fat, organicsolvent, ionic or nonionic thickening agent, softener, antioxidant,anti-free-radical antioxidant, opacifying agent, stabilizing agent,emollient, silicone, α-hydroxy acid, anti-foaming agent, hydratingagent, vitamin, fragrance, preservative, surfactant, filler,sequestering agent, polymer, propellant, insect repellent, basifying oracidifying agent, dye, colorant, or mixture thereof.
 15. Thesunscreen/cosmetic composition as defined by claim 1, comprising anonionic vesicle dispersion, emulsion, cream, milk, gel, cream gel,ointment, suspension, dispersion, powder, solid stick, foam or spray.16. The sunscreen/cosmetic composition as defined by claim 1, comprisinga makeup.
 17. The sunscreen/cosmetic composition as defined by claim 16,comprising an anhydrous or aqueous solid or paste, emulsion, suspension,or dispersion.
 18. The sunscreen/cosmetic composition as defined byclaim 1, comprising a shampoo, lotion, gel, emulsion, nonionic vesicledispersion, hair lacquer, or rinse.
 19. The sunscreen/cosmeticcomposition as defined by claim 1, having a sun protection factor of atleast
 2. 20. A method for protecting human skin and/or hair against thedeleterious effects of ultraviolet irradiation, comprising topicallyapplying thereto an effective amount of the sunscreen/cosmeticcomposition as defined by claim
 1. 21. A method for protecting humanskin and/or hair against the deleterious effects of solar radiation,comprising topically applying thereto an effective amount of thesunscreen/cosmetic composition as defined by claim 1.